Theoretical calculation of parameters of three-parameter characteristics method for liquid phases. III. Polarity parameter and phase classification
DOI:
https://doi.org/10.17308/sorpchrom.2026.26/14175Keywords:
adsorption energy, intermolecular interactions, gas chromatography, stationary phase, dipole moment, po-larity.Abstract
The selectivity of separation in gas chromatography is determined by the nature of the stationary phase. Within the framework of the intermolecular interaction model previously proposed by the authors and the theoretical method for three-parameter characterization of chromatographic stationary liquid phases developed on its basis, a quantitative assessment is made of the ability of molecules to participate in dispersion, dipole-dipole interactions, and hydrogen bonds. This method has proven effective in describing the properties of stationary phases of various classes. The properties of stationary phases and sorbate molecules are described by two selectivity characteristics: polarity and hydrophilicity, which can be calculated using the direct problem based on the structural formula of the substance and the inverse problem based on experimental data in the form of the Kovacs retention indices or Rohrschneider-McReynolds constants. The model used is internally consistent, and both calculation methods are equally valid. A convenient and visual method for classifying stationary phases using the three-parameter characteristic method is the selectivity map. Combined with the principle of property similarity, it is used to select the stationary phase most selective for given sorbates; this selection can be made without experimentation.
The primary tool for describing intermolecular interactions was the theory of generalized charges, previously developed at the Sorption Methods Laboratory of the Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences. This theory provides an ab initio description of non-polar forces without relying on the principle of additivity of atom-atom potentials. A brief summary of the main points of the theory of generalized charges and the derivation of the corresponding contribution to the energy of intermolecular interactions were given in the first article of this series. As follows from statistical analysis of chromatographic data, the traditional concept of polarity of a substance includes two independent dimensions, caused by electrostatic interactions on one hand, and hydrogen bonding on the other. The contribution of hydrogen bonds to the energy of intermolecular interactions and the method for determining the corresponding parameter, called "hydrophilicity," were discussed in the second article of this series. This paper is devoted to determining the dipole moments and polarity parameters of substances, including chromatographic stationary phases, and is the third and final article in the series. The article examines methods for determining the polarity of substances based on their structural formulas. The results of dipole moment calculations and polarity characteristics for substances of various classes, including gas chromatographic stationary phases, are presented. In the final section, the data from all three articles in the series are presented in the form of a selectivity map for organic and organosilicon gas chromatographic stationary phases.
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